Solvent-free Solid Phase Research Articles

Cu2CoSnS4 electrocatalyst embedded paper working electrodes for efficient, stable, pH universal, and large-current-density hydrogen evolution reaction

In this study, practical application for the industrial-scale hydrogen evolution reaction (HER) process is established using sustainable Cu2CoSnS4 embedded in paper-working electrodes. The Cu2CoSnS4 is produced using a solvent-free solid-phase approach. The effect of a wide pH range of electrolytes on working electrodes for hydrogen evolution reactions is also investigated. The Cu 2CoSnS4 embedded paper-working electrodes exhibit goodelectrocatalytic activity for hydrogen evolution reaction with low overpotential values of 233, 310, and 261 mV vs RHE at 10 mA/cm 2 in 0.5 M H2SO4,1 M KOH, and 1 M PBS, respectively. These designed electrodes exhibit high double-layer capacitance and electrochemical surface area for a wide pH range. In acidic, alkaline and neutral environments, the catalyst-embedded paper electrodes explicit high turnover frequencies of 2.15 s−1, 2.75 s−1, and 2.11 s−1, respectively. The temperature-dependent hydrogen evolution reaction is studied to calculate the activation energy of the cathodic electrode. Utilising chrono-amperometry for about 118 h in an acidic media, which shows that electrodes have a high degree of stability. In comparison to other previously reported work on catalyst-embedded electrodes, the Cu2CoSnS4 embedded paper-working electrodes offer excellentpotential for HER activity across a wide pH range and are suitable for industrial application.

Isotope-labeling in situ derivatization and HS-SPME arrow GC-MS/MS for simultaneous determination of fatty acids and fatty acid methyl esters in aqueous matrices.

Fatty acids (FAs) and fatty acid methyl esters (FAMEs) co-occur in many samples, and analysis of both substance classes is frequently of high interest. To this end, this study introduces the first method for simultaneous determination of FAs and FAMEs including fully automated solvent-free solid-phase microextraction (SPME) arrow headspace extraction combined with isotope-labeling in situ FA derivatization with deuterated methanol (CD3OD). By using the chromatographic isotope effect (ΔRt = 0.03min) and the + 3m/z mass shift, FAs can be selectively differentiated from the FAMEs during gas chromatography tandem-mass spectrometry (GC-MS/MS) operated in the multiple reaction monitoring (MRM) aquisition mode. Additionally, an approach is presented to predict the retention times of deuterated compounds. Optimization of the derivatization conditions was accomplished by design of experiments and found to be 20min, 50°C, 4v/v% CD3OD, and pH 2.1. During method validation, FAs and FAMEs were calibrated in different concentration ranges by standard addition in five real matrices and ultrapure water leading to good linearities and method detection limits for FAs ranging from 1-30µgL-1 and for FAMEs from 0.003-0.72µgL-1. FAs and FAMEs were detected in real samples from surface water, wastewater treatment plant effluent, and three different bioreactor samples and could be quantified in concentrations ranging from 2-1056µgL-1 for FAs and 0.01-14µgL-1 for FAMEs.

Organic solvent-free solid-phase extraction of acetamiprid in food samples using Strep-Tag system integrated apta-magnetic sorbents

A novel magnetic sorbent, named ABA-(Strep-tag II)-STMB, was prepared by modifying the acetamiprid-binding aptamer (ABA) onto Strep-Tactin-coated magnetic beads (STMBs) via Strep-tag II. The integration of the Strep-tag system allows the elution of the target by the addition of D-biotin, which can compete with Strep-tag II for the Strep-Tactin sites on the magnetic beads, instead of organic solvents. The sorbent showed good selectivity and reusability, and the extraction efficiency could still reach 90.5 % after 8 reuses. Under the optimized conditions, the developed magnetic solid-phase extraction (MSPE) method exhibited good linearity in the range of 0.1–100 μM, with the limits of detection (LOD) of 0.017–0.019 μM, and the limits of quantification (LOQ) of 0.057–0.066 μM. The relative standard deviations (RSDs) were below 5.51 %. The spiked recoveries were 84.4 %–96.0 %. The analysis results were in good agreement with those of the QuEChERS method.

Synthesis, Characterization, Pharmacogenomics, and Molecular Simulation of Pyridinium Type of Ionic Liquids and Their Applications.

Substituted pyridinium bromides are prepared by conventional and solvent-free greener methods. The solvent-free solid-phase (greener) method is superior to the conventional method because of its nontoxic nature, simple reaction setup procedure, and twenty times less time consumption. Column chromatography and toxic organic solvents are avoided. Substituted pyridinium salts 1-2(a-c) show excellent catalytic response in the preparation of β-amino carbonyl derivatives using the conventional approach. Pharmacokinetics is very important in target validation and in shifting a lead compound into a drug. The physicochemical properties discussed here can be used effectively in the drug designing candidate, which is a cumbersome process in clinical research. In addition, molecular simulations are demonstrated, and compounds 1-2(a-c) possess the most potent VEGFR-2 kinase protein inhibitory activities, and most interestingly, compound 2a strongly binds and regulates the VEGFR-2 kinase activity in therapeutic approaches and cancer prevention.

Solid–solid chemical bonding featuring targeted defect passivation for efficient perovskite photovoltaics

A solvent-free solid-phase technique was developed for the targeted defect passivation of perovskite films, resulting in an ultra-high PCE of 25.2%.

Monometallic, bimetallic, and trimetallic chalcogenide-based electrodes for electrocatalytic hydrogen evolution reaction

Cu2CoSnS4, Cu2SnS3, Cu2CoS4, Co2SnS3, Cu2S, CoS2, and SnS2 were synthesized using a one-step solvent-free solid-phase approach. The surface structure, morphology, and composition were characterized using an X-ray diffractometer (XRD), Fourier-Transform Infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and X-ray Photoelectron Spectroscopy (XPS). The characterizations reveal pure phase formation and porous morphology. Further, the Hydrogen evolution reaction was performed using Cu2CoSnS4, Cu2SnS3, Cu2CoS4, Co2SnS3, Cu2S, CoS2, and SnS2-based electrodes. Amid all electrocatalysts, Cu2CoSnS4 shows an excellent hydrogen evolution reaction with a low overpotential of −192.1 mV at −10 mA/cm2 in 0.5 M H2SO4. And higher current density. Cu2CoSnS4 also shows a lower Tafel slope of 98.6 mV/dec and charge transfer resistance than mono and bimetallic chalcogenide-based electrodes. The Cu2CoSnS4 exhibit very good stability for ∼22 h at −10 mA/cm2 current density in 0.5 M H2SO4.

A flexible Li2SnO3-coupled PEO-based single-ion conducting composite solid-state electrolyte for highly-stable Li metal batteries

Development of all-solid-state lithium-ion batteries (ASSLBs) with potentially high energy density and safety is critical for next-generation energy storage devices. In this work, a low-cost flexible Li2SnO3(LSO)-coupled PEO-based composite single-ion conducting polymer solid-state electrolyte (CSIPE) was prepared by a simple solvent-free solid-phase method. The obtained LSO-coupled CSIPE exhibited a high ionic conductivity of 5.59 × 10−4 S cm−1 at 60 °C with a high lithium ion transference number of 0.54 and an electrochemical stability window as high as 5.28 V. In addition, the results based on Vogel-Tammann-Fulcher (VTF) model and differential scanning calorimetry (DSC) measurements indicated that the presence of LSO reduced the activation energy for lithium ion migration and the crystallinity of the polymer matrix to provide channels and flexible polymer chains for the transportation of lithium ions. Moreover, the fabricated lithium metal anode based full cell worked stably for more than 100 cycles maintaining a high specific capacity of 127.1 mAh g−1 and a specific capacity retention ratio of 96.5% at a high cycling rate of 0.5 C. While, the CSIPE also demonstrated an excellent rate performance and outstanding adaptation to cathodes. Furthermore, the obtained LSO-coupled CSIPE remained stable even at a temperature as high as 322 °C without thermal runaway, and worked under different current densities for 450 h without short-circuiting, indicating good interfacial stability to ensure the safety of the batteries. It is expected that this LSO-coupled CSIPE is a promising substitute for liquid electrolytes with broad commercial prospects.

Assessment of marine sediment remediation efficiency with SPME-based passive sampling measurement

Passive sampling has been shown to be a suitable procedure to assess the risk of contaminated sediments through the measurement of freely dissolved concentrations (CFree) and remedial actions involving amendments such as activated carbon (AC). Here we report results of the application of simple, solvent-free solid phase micro extraction methodology (SPME) to assess the performance of different materials for the remediation of selected Norwegian harbour sediments contaminated with polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). AC amendments enabled a reduction of the availability of PAHs and/or PCBs by a factor of ten to over one hundred in Aker Brygge sediments (Oslo) and sediments from Elkembukta, impacted by industrial emissions of PAHs with/from coal tar pitch. Another material, anthracite, slightly less effective in this set of experiment than AC, showed nonetheless great promise as capping material. The SPME data are put in perspective with equilibrium measurements of CFree for PAHs and organochlorines with silicone rubber in other Elkembukta sediments collected in the vicinity of those used for the remediation experiments. A reduction of sediment Cfree for pyrene, benzo[a]pyrene and benzo[ghi]perylene in inner Elkembukta sediment from on average 407, 6.3 and 0.82 ng L−1 to values of/or below 1.3, 0.15 and 0.076 ng L−1, respectively can be expected upon remediation with AC. For the outer, less contaminated Elkembukta sediment, Cfree would reduce from 36, 0.81 and 0.13 ng L−1 to value of or below 0.06, 0.03 and 0.005 ng L−1 for these three compounds, respectively. Differences in pattern of PAH and organochlorine contamination of inner and outer Elkembukta sediments are discussed.

Solid-phase oxalic acid leaching of natural red palygorskite-rich clay: A solvent-free way to change color and properties

A simple, efficient and economical solvent-free solid-phase oxalic acid (OA) leaching process was employed to treat natural red palygorskite-rich clay (Pal-R-C). The effect of OA leaching parameters (e.g., dosage of OA, reaction temperature and reaction time) on the color and physicochemical properties of Pal-R-C was studied, and the application potential of the acid-activated Pal-R-C in polymer composite was studied by evaluating its reinforcing role on sodium alginate (SA) film. The results indicate that the solid-phase OA leaching reaction may dissolve red hematite and other acid-soluble impurities. Mössbauer spectra analysis confirmed that the red color of clay is mainly resulting from the hematite impurity existed in the mixed clay, instead of octahedral iron ions, and the removal of hematite caused the color change of clay from red to white. The increase of OA dosage made more iron oxide being leached, leading to the further increase of the whiteness of product. The reaction process occurred at melting state of OA is relatively static, and could be easily controlled by tuning the reaction conditions. After treatment with 60% of OA, the total iron content of Pal-R-C decreased by 69%, and the color of Pal-R-C was transformed completely from red to white, as confirmed by the change of L* value from 64.4 to 84.4, a* value from 13.9 to 0.4, and b* value from 24.7 to 5.2. SEM and TEM results indicate the OA leaching process does not obviously damage the crystalline structure and morphology of Pal rod and other minerals. The specific surface area increased from 40.27 to 62.79 m2/g after the OA leaching process. The whitened Pal-R-C can improve the tensile strength of polymer films more effectively than raw Pal-R-C. This paper would pave a foundation for extending the large-scale applications of natural abundant red clay resource.

Fast determination of octinoxate and oxybenzone uv filters in swimming pool waters by gas chromatography/mass spectrometry after solid‐phase microextraction

A fast gas chromatography/mass spectrometry method was developed and validated for the analysis of the potential endocrine disrupters octinoxate and oxybenzone in swimming pool water samples based on the solvent-free solid-phase microextraction technique. The low-pressure gas chromatography/mass spectrometry method used for the fast identification of UV filter substances was compared to a conventional method in terms of sensitivity and speed. The fast method proposed resulted in 2 min runs, leading to an eightfold decrease in the total analysis time and a sevenfold improvement in detection limits. The main parameters affecting the solid-phase microextraction process were also studied in detail and the optimized conditions were as follows: fiber coating, polyacrylate; extraction mode, direct immersion; extraction temperature, 25°C; sample volume, 5 mL; extraction time 45 min; pH 6.5. Under the optimized conditions, a linear response was obtained in the concentration range of 0.5-25 μg/L with correlation coefficients in the range 0.990-0.999. The limits of detection were 0.17-0.29 μg/L, and the recoveries were 80-83%. Combined method uncertainty was assessed and found to be less than 7% for both analytes for concentrations equal to or higher than 5 μg/L. Pool water samples were analyzed to demonstrate the applicability of the proposed method. Neither octinoxate nor oxybenzone were detected in the swimming pool water samples at concentrations above the respective limits of detection.

Magnetic nanoparticles solid phase extraction based on the formation of supramolecular mixed hemimicelle aggregates for the determination of naproxen in biological fluids using high‐performance liquid chromatography‐UV

A novel, fast, sensitive and practically solvent-free solid phase extraction method based on the adsorption of cetyltrimethylammonium bromide onto the surface of Fe3O4 nanoparticle adsorbent was developed for the quantitative determination of naproxen in biological fluids. The adsorbent was characterised by a transmission electron microscope, an X-ray diffractometer and Fourier transform infrared spectroscopy techniques. The main factors affecting the adsorption efficiency of the analyte such as the surfactant amount, pH value, desorption conditions, extraction and desorption time, sample volume, amount of Fe3O4 nanoparticles and ionic strength were evaluated and optimised. No clean-up steps were necessary for the determination of the drug in biological matrices because of the direct analysis of the eluate by liquid chromatography/UV, which is matrix-effect free. Under optimum conditions, naproxen was quantitatively determined and the linear range of the method was 0.1–700 ng ml−1 with a correlation coefficient of 0.9993. An enrichment factor of 198 was obtained by extracting 200 ml of the sample solution. The detection limit was 0.01 ng ml−1 and relative standard deviations (RSD %) for 20 and 150 ng ml−1 were obtained as 2.9 and 2.3%, respectively. Finally, the proposed method was successfully applied to the determination of naproxen in human plasma and urine samples.

Chain-Growth Insertion Polymerization of 1,3-Diethynylbenzene High Internal Phase Emulsions into Reactive π-Conjugated Foams

The π-conjugated micro/macroporous polyacetylene-type polyHIPE foams were synthesized for the first time by a chain-growth insertion polymerization of high internal phase emulsions (HIPEs). In the first step, the π-conjugated polyHIPE foams were prepared by polymerization of 1,3-diethynylbenzene HIPEs using [Rh(nbd)acac] complex as a catalyst. The π-conjugated polyHIPE foams consist of ethynylphenyl-substituted polyene main chains which are cross-linked by the 1,3-phenylene linkers. In the second step, the foams were chemically and thermally postmodified by applying the alkyne–azide cycloaddition reaction and the solvent free solid phase hyper-cross-linking at temperature of 280 °C. Thus, obtained polyacetylene-type polyHIPE foams exhibit hierarchically structured micro/macroporous morphology with sizes of the macropores and interconnecting pores of 3.4 ± 0.3 μm (or 4.8 ± 0.8 μm) and 0.96 μm (or 1.1 μm), respectively, wherein a substantial volume of micropores is also found within the macroporous walls as revealed by the calculations from the t-plots. The BET (Brunaer–Emmett–Teller) surface area of up to 110 and 380 m2 g–1 was determined before and after solid phase hyper-cross-linking, respectively.

Dehydration behaviour of hydrates

AbstractImmersing a crystalline solvate in a suitable anti‐solvent can induce phase transformation to solvent‐free solid phase. In certain cases the solvent‐mediated phase transition results in the generation of hollow, tubular structures. Both the tube dimensions of sodium‐2‐keto‐L‐gulonate anhydrate (skga) and the dehydration kinetics of sodium‐2‐keto‐L‐gulonate monohydrate (skgm) can be modified by the antisolvent employed. An explanation for the variable dehydration behaviour of skgm in the antisolvents is presented here. Furthermore, other crystalline hydrates were dehydrated in dry methanol. Providing an operational window can be found, any hydrate material could possibly find use in the production of tubes (micro‐ or nanotubes for different applications). The experimental conditions selected (dry methanol as antisolvent, dehydration temperature at 25 °C) for the dehydration did not lead to the anhydrate tube growth for all hydrates investigated. Based upon the results presented here a first hypothesis is presented to explain this effect. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Supramolecular solid-phase extraction of ibuprofen and naproxen from sewage based on the formation of mixed supramolecular aggregates prior to their liquid chromatographic/photometric determination

Sorbents made up of sodium dodecyl sulphate (SDS) hemimicelles, formed onto γ-alumina, were proposed for the quantitative and practically solvent-free solid-phase extraction (SPE) of ibuprofen and naproxen from sewage samples. The formation of drug–SDS mixed aggregates was proved by the pseudophase separation model and their composition as a function of the amount of drug was calculated. The overall hemimicellar SPE procedure consumed only 0.6 mL of methanol since non-organic solvent was required for cartridge conditioning and the drugs were completely eluted using 2 mL of a 0.3 M NaOH:methanol (70:30, v/v) solution. Breakthrough volumes of around 0.75 L and above 1 L were obtained for naproxen and ibuprofen, respectively. No clean-up steps were necessary for the determination of these drugs in sewage because the direct analysis of the eluates by liquid chromatography/UV was matrix effect-free. The identification of the analytes was based on retention times and UV spectra and it was confirmed by on-line fluorescence detection. The detection limits for naproxen and ibuprofen were 0.8 and 9 ng L −1 in wastewater influents and 0.5 and 7 ng L −1 in effluents, respectively. These limits were similar to or lower than those achieved by methods based on conventional sorbents (e.g. C 18–silica or polymeric resins), which invariably require the evaporation of the eluates. The accuracy and precision of the proposed method were assessed by analysing influent and effluent wastewater samples spiked with 2 and 0.4 μg L −1 of each analyte, respectively. The recoveries obtained and the corresponding standard deviations were in the ranges 93–101% and 2–9%. The method was applied to the determination of the target drugs in wastewater from three sewage treatment plants (STPs) in the south of Spain. The concentration of ibuprofen and naproxen ranged between 2.0 and 7.4 μg L −1 and 0.9 and 3.3 μg L −1 in influents and 0.4 and 1.4 μg L −1 and 0.2 and 0.8 μg L −1 in effluents, respectively.

Dual-Injection System with Multiple Injections for Determining Bidimensional Retention Indexes in Comprehensive Two-Dimensional Gas Chromatography

A new instrumental approach for collection of retention index data in the first (1D) and second (2D) dimensions of a comprehensive two-dimensional (2D) gas chromatography (GCxGC) experiment has been developed. First-dimension indexes were determined under conventional linear programmed temperature conditions (Van den Dool indexes). To remove the effect that the short secondary column imposes on derived 1D indexes, as well as to avoid handling of pulsed GCxGC peaks, the proposed approach uses a flow splitter to divert part of the primary column flow to a supplementary detector to simultaneously generate a conventional 1D chromatogram, along with the GCxGC chromatogram. The critical 2D indexes (KovAts indexes) are based upon isovolatility curves of normal alkanes in 2D space, providing a reference scale against which to correlate each individual target peak throughout the entire GCxGC run. This requires the alkanes to bracket the analytes in order to allow retention interpolation. Exponential curves produced in the 2D separation space require a novel approach for delivery of alkane standards into the 2D column by using careful solvent-free solid-phase microextraction (SPME) sampling. Sequential introduction of alkane mixtures during GCxGC runs was performed by thermal desorption in a second injector which was directly coupled through a short transfer line to the entrance of the secondary column, just prior to the modulator so that they do not have to travel through the 1D column. Thus, each alkane mixture injection was quantitatively focused by the cryogenic trap, then launched at predetermined times onto the 2D column. The system permitted construction of an alkane retention map upon which bidimensional indexes of a 25-perfume ingredient mixture could be derived. Comparison of results with indexes determined in temperature-variable one-dimensional (1D) GC showed good correlation. Plotting of the separation power in the second dimension was possible by mapping Trennzahl values throughout the 2D space. The methodology was applied to the separation of a standard mixture composed of 25 analytes (very diverse in polarity and structure) suspected to be allergens in perfume samples. The method will allow straightforward determination of temperature-variable retention indexes of target analytes.

Detection of 2,4,6-trichloroanisole in microorganism-free irradiated raisins by solid-phase microextraction and GC-MS

The occurrence of 2,4,6-trichloroanisole (TCA) in nonprocessed dry-on-the-vine (DOV) and Thompson seedless irradiated raisins extracted by solvent-free solid-phase microextraction (SPME) was confirmed using gas chromatography/mass spectrometry. The 42 kGy (kilo Gray) dose irradiated DOV and Thompson seedless raisins incubated in five growth media were shown to be free of microorganisms. The quantity of TCA in the irradiated raisins was 0.39±0.05 ng/kg compared with 0.56±0.17 ng/kg in nonirradiated samples. The observation supports the view that raisins biosynthesize a minute but detectable quantity of TCA. The SPME fiber (divinylbenzene/carboxen/polydimethylsiloxane) method was simpler and quicker than the Likens–Nickerson extraction method for TCA determination. The biochemical mechanism of TCA production in raisin grape is unknown, but information in the biochemical literature of abundant phenolic substrates in grape berry, the presence of methyltransferases in Vitis tissues and of a chlorinating system provides a plausible basis for further investigation of the process.

Determination of polycyclic aromatic hydrocarbons in waste water by off-line coupling of solid-phase microextraction with column liquid chromatography

A new method for the determination of polycyclic aromatic hydrocarbons (PAHs) in waste water using solvent-free solid-phase microextraction (SPME) is described. The PAHs are extracted with a 100 μm polydimethylsiloxane (PDMS) fiber, desorbed in 40 μl acetonitrile and measured with LC and fluorescence detection. The detection limits of this very simple method under the given conditions (extraction from 5 ml sample, extraction time 1 h) are in the range of 1–6 ng l −1. The standard deviations ( n=6) at a concentration level of 0.8 μg l −1 are between 1.8 and 14.4%. The procedure was used for the determination of PAHs in contaminated water samples.

5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine: characterization of the solvent-free solid phase and interaction with ammonia and water

The 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine (LH, C11H3N7), previously characterized as the 2:1 1-chloronaphthalene adduct, has been further investigated as a solvent-free solid phase. Strong intermolecular interactions take place in this phase, as revealed by the optical spectra of evaporated LH thin films (lambda;max=615 and 570 nm) compared to the optical spectrum of LH in solution (lambda;max=580 nm). 13C NMR spectra also support the occurrence of intermolecular attractive CN group interactions in the solid state. X-Ray diffraction patterns indicate that the controlled sublimation process of LH (Tsubl=200 °C, 10–6 mmHg) leads to films composed of highly oriented crystallites, with two main sets of diffracting planes parallel to the film surface. The refractive index of LH as an evaporated thin film has also been determined in the 400–800 nm spectral range (n=1–2). LH interacts with ammonia and/or water in the gas phase. In the first case the acid–base reaction (LH+NH3 ⇄L′·NH4+) occurs. The resulting L′ anion (L′C11H2N7–) is the 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (A, lambda;max=525 nm) or the isomer 1,2,6,7-tetracyano-3,5-dihydro-3,5-diiminopyrrolizinide (B, lambda;max=680 nm), depending on the relative amount of water to ammonia in the gas phase. This reaction is driven by the hydrogen bonding of NH4+ to B and/or to water. In the second case a fast proton scrambling occurs.

Hydrogenation of fullerenes C 60 and C 70 in the presence of hydride-forming metals and intermetallic compounds

Hydrogen-absorbing intermetallics generate very pure and chemically active hydrogen. In this communication we report on the use of this property for hydrogenation of fullerenes (C 6 0, C 70) in solvent-free solid-phase systems. Fullerene hydrides with high contents of hydrogen (24–26 H atoms per fullerene molecule) have been obtained by hydrogenation of solid-phase mixtures of fullerite with either intermetallic compounds LaNi 5, LaNi 4.65Mn 0.35, CeCo 3 or V and Pd metals in relatively mild conditions, a hydrogen gas pressure of 1.0–2.5 MPa and 573–673 K. The mechanochemical treatment of initial solid compositions and repeated `hydrogenation–dehydrogenation' cycling are both essential to ensure the highest performance of the systems studied, thus emphasizing the importance of a highly developed contact surface between two solid phases and indicating a probable formation of metal–carbon bonds. The fullerene hydrides thus obtained decompose in all cases at 800 K, liberating hydrogen gas. After further heating up to 1000 K vanadium reacts with fullerenes yielding a cubic phase of vanadium carbide. Intermetallics under the same conditions react with fullerenes by disintegrating their cage and producing a metallic phase of the corresponding 3d metal. In the case of palladium that reaction is not observed and the fullerene remains intact. The nature of the transformations in the mechanical mixtures of fullerite with metals or intermetallics is discussed.